CA1269197A - Process for activation of titanium and vanadium catalysts useful in ethylene polymerization - Google Patents
Process for activation of titanium and vanadium catalysts useful in ethylene polymerizationInfo
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- CA1269197A CA1269197A CA000530090A CA530090A CA1269197A CA 1269197 A CA1269197 A CA 1269197A CA 000530090 A CA000530090 A CA 000530090A CA 530090 A CA530090 A CA 530090A CA 1269197 A CA1269197 A CA 1269197A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
Abstract
PROCESS FOR ACTIVATION OF TITANIUM AND VANADIUM
CATALYSTS USEFUL IN ETHYLENE POLYMERIZATION
ABSTRACT
A process for activating a titanium or vanadium compound and producing polyethylene comprising (i) dissolving a divalent magnesium halide and a Lewis acid having the formula RmA1Xn or RmBXn wherein R is an alkyl or aromatic radical, each radical having 1 to 12 carbon atoms and each R being alike or different; X is a halogen atom; m is an integer from 0 to 3; n is an integer from 0 to 3; and m+n equals 3, in an excess of electron donor compound selected from the group consisting of alkyl esters of alkyl and aromatic carboxylic acids and alkyl and cycloalkyl ethers, each compound having 2 to 12 carbon atoms, in such a manner that a magnesium halide/Lewis acid/electron donor complex is formed; (ii) separating the complex from excess electron donor compound; and (iii) introducing (a) the complex, the titanium or vanadium compound, and a hydrocarbyl aluminum compound and (b) ethylene into a reactor in such a manner that the titanium or vanadium compound is activated and polyethylene is produced.
CATALYSTS USEFUL IN ETHYLENE POLYMERIZATION
ABSTRACT
A process for activating a titanium or vanadium compound and producing polyethylene comprising (i) dissolving a divalent magnesium halide and a Lewis acid having the formula RmA1Xn or RmBXn wherein R is an alkyl or aromatic radical, each radical having 1 to 12 carbon atoms and each R being alike or different; X is a halogen atom; m is an integer from 0 to 3; n is an integer from 0 to 3; and m+n equals 3, in an excess of electron donor compound selected from the group consisting of alkyl esters of alkyl and aromatic carboxylic acids and alkyl and cycloalkyl ethers, each compound having 2 to 12 carbon atoms, in such a manner that a magnesium halide/Lewis acid/electron donor complex is formed; (ii) separating the complex from excess electron donor compound; and (iii) introducing (a) the complex, the titanium or vanadium compound, and a hydrocarbyl aluminum compound and (b) ethylene into a reactor in such a manner that the titanium or vanadium compound is activated and polyethylene is produced.
Description
~69~3i7 PROCESS FOR ACTIVATION OF TITANIUM AND VANADIUM
CATAL STS USEFUL IN ETHYLENE POLYMERIZA~ION_ Technical Field This invention relates to a process for the activation of an ethylene polymerization catalyst, and an activator therefor.
Backqround Art A typical ethylene polymerization catalyst is prepared by forming a precursor from a magnesium compound, a titanium compound, and an electron donor compound; diluting the precursor with an inert carrier material; and activating the precursor by introducing an organoaluminum compound. The process is described in United States patents 4,302,565;
4,302,566; and 4,303,771. The magnesium and titanium compounds are dissolved in the electron donor compound (solvent) at a temperature ranging from ambient to below the boiling point of the electron donor. The order of addition to the electron donor compound is not important to the result, i.e., one or the other of the magnesium and titanium compounds can be added first or they can be added together. The dissolution in the electron donor compound can be enhanced by slurrying or refluxing. After the magnesium and titanium compounds are dissolved, the resulting product is isolated by crystallization or precipitation with a hydrocarbon such as hexane, isopentane, or benzene.
The crystallized or D-14,119 ~Z~91~7 precipitated product is dried and recovered as fine, free-flowing particles. The magnesium/titanium based composition is then mixed with, or impregnated into, an inert carrier material. The carrier is generally a solid, particulate, porous material such as silica.
In order for the magnesium/titanium based composition to be useful as a polymerization catalyst, it must be activated with a compound capable of transforming the magnesium/titanium atoms to a state which will effect the desired polymerization reaction. Activation is accomplished by the addition of an organoaluminum compound.
Partial activation, if desired, is effected outside of the polymerization reactor by introducing the catalyst composition and the organoaluminum into a solvent. Complete activation is then carried out in the reactor as described in United States patent 4,383,095.
While the magnesium/titanium based catalyst compositions have proved to be satisfactory ethylene polymerization catalysts, there is a continuing effort to improve on the catalysis aspect of ethylene polymerization and, more particularly, to improve the technique for catalyst activation.
Disclosure of the Invention An object of this invention, therefore, is to provide a process for the activation of known ethylene polymerization catalysts, such as titanium D-14,119 ~2~ 7 or vansdium compounds, whereby an activated catalyst is prepared much more rapidly and simply than by following the route to the activated magnesium/
titanium based cstalyst composition heretofore discussed.
Other ob~ects and advantages will become apparent hereafter.
According to the present invention, process for activating a titanium or vanadium compound and producing polyethylene has been discovered comprising (i) dissolving a divalent magnesium halide and a Lewis acid having the formula RmAlXn or RmBXn wherein R is an alkyl or aromatic radical, each radical having 1 to 12 carbon atoms and each R being alike or different; X is a halogen atom; m is an integer from 0 to 3; and m+n equals 3, in an excess of electron donor compound selected from the group consisting of alkyl esters of alkyl snd aromatic carboxylic acids and alkyl and cycloalkyl ethers, each compound having 2 to 12 carbon atoms, in such a manner that a magnesium halidelLewis acid/electron donor complex is formed;
(ii) separating the complex from excess electron donor compound; and (iii) introducing (a) the complex, the titanium or vanadium compound, and a hydrocarbyl aluminum compound and (b) ethylene into a reactor in such a manner that the titanium or vanadium compound is activated and polyethylene is produced.
Detailed DescriPtion Titanium or vanadium compounds of lnterest here are commonly used as catalyst components in the `` ~269~7 polymerization of ethylene. Typical titanium compounds have the formula Ti(OR)nX4_n wherein R
is a hydrocarbyl group having 1 to 14 carbon atoms or a COR' radical wherein R' is a hydrocarbyl group having 1 to 14 carbon atoms; X is a halide radical;
and n is an integer from 0 to 4. Examples of titanium compounds are TiCl4; TiBr4; TiI4;
Ti(OCH3)C13; Ti(OC6H5)C13;
Ti(OCOCH3)C13; Ti(OCOC6H5)C13; Ti(OC2H5)C13;
( C2H5)2Cl2; Ti(C3H7)2C12; Ti(OC2H5)3Cl;
Ti(OC6H5)3Cl, Ti(OC2H5)4; Ti(oC3H7)4;
Ti(oC4Hg)4; Ti(oC6H13)4, Ti(OC6Hll)4;
( 8H17)4; Ti(CH2(C2H5) CHC4Hg)4;
Ti(OCgH19)4; Ti[OC6H3(CH3)2]4;
( 3)2(OC4H9)2; Ti(OC3H7)3(OC4Hg);
( 2 5)2(OC4Hg)2; Ti(OC2H4OCH3)4; and Ti~OC2H4Cl)4. Examples of vanadium compounds are VC14, VC13, VOCl3, triisobutyl vanadate, and vanadiumltris-acetyl acetonate. Other suitable vanadium compounds are mentioned in United States patents 3,956,255 and 4,370,455.
The electron donor solvents used in the process are organic compounds, liquid at temperatures in the range of about 0C to about 200C, in which the magnesium halide and defined Lewis acids are soluble. The electron donor solvents are also known as Lewis bases.
The electron donor compounds are selected from the group consisting of alkyl esters of alkyl and aromatic carboxylic acids and alkyl and cycloalkyl ethers, each compound having 2 to 12 D-14,119 ~Z~9~7 carbon atoms. Among these electron donor compounds the preferable ones are alkyl esters of saturated alkyl carboxylic acids having 1 to 4 csrbon atoms;
alkyl esters of aromatic carboxylic acids having 7 or 8 carbon atoms; alkyl ethers having 2 to 8 carbon atoms, preferably 4 or 5 carbon atoms; and cycloalkyl ethers having 4 or 5 carbon atoms;
preferably mono- or di-ethers having 4 c~rbon atoms. The most preferred of these electron donor compounds include methyl formate, ethyl acetate, butyl acetate, ethyl ether, tetrahydrofuran, and dioxane. Other examples of electron donor compounds are di-n-propy~ ether, dibutyl ether, ethyl formate, methyl acetate, ethyl anisate, ethylene carbonate, tetrahydropyran, and ethyl propionate.
The divalent magnesium halide can be represented by the formula MgX2 wherein X ~s selected from the group consisting of Cl, Br, and I.
Suitable magnesium compounds include MgC12, MgBr2, and MgI2. Anhydrous MgC12 is particularly preferred.
The Lewis acids are, as noted above, those having the formula RmAlXn or RmBXn wherein R is an alkyl or aromatic radical, each radical having 1 to 12 carbon stoms and each R being alike or different; X is a halogen atom; M is an integer from O to 3; n is an integer from O to 3; and m+n equals 3. Examples of alkyl radicals are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, ~l269~7 pentyl, neopentyl, hexyl, 2-methylpentyl, heptyl, octyl, isooctyl, 2-ethylhexyl, 5,5-dimethylhexyl, nonyl, decyl, isodecyl, undecyl, and dodecyl.
Example of aromatic radicals are: phenyl, phenethyl, methoxyphenyl, benzyl, tolyl, xylyl, naphthyl, naphthal, and methylnaphthyl. Examples of halogens are chlorine, bromine, and iodine.
Preferred Lewis acids are AlC13,
CATAL STS USEFUL IN ETHYLENE POLYMERIZA~ION_ Technical Field This invention relates to a process for the activation of an ethylene polymerization catalyst, and an activator therefor.
Backqround Art A typical ethylene polymerization catalyst is prepared by forming a precursor from a magnesium compound, a titanium compound, and an electron donor compound; diluting the precursor with an inert carrier material; and activating the precursor by introducing an organoaluminum compound. The process is described in United States patents 4,302,565;
4,302,566; and 4,303,771. The magnesium and titanium compounds are dissolved in the electron donor compound (solvent) at a temperature ranging from ambient to below the boiling point of the electron donor. The order of addition to the electron donor compound is not important to the result, i.e., one or the other of the magnesium and titanium compounds can be added first or they can be added together. The dissolution in the electron donor compound can be enhanced by slurrying or refluxing. After the magnesium and titanium compounds are dissolved, the resulting product is isolated by crystallization or precipitation with a hydrocarbon such as hexane, isopentane, or benzene.
The crystallized or D-14,119 ~Z~91~7 precipitated product is dried and recovered as fine, free-flowing particles. The magnesium/titanium based composition is then mixed with, or impregnated into, an inert carrier material. The carrier is generally a solid, particulate, porous material such as silica.
In order for the magnesium/titanium based composition to be useful as a polymerization catalyst, it must be activated with a compound capable of transforming the magnesium/titanium atoms to a state which will effect the desired polymerization reaction. Activation is accomplished by the addition of an organoaluminum compound.
Partial activation, if desired, is effected outside of the polymerization reactor by introducing the catalyst composition and the organoaluminum into a solvent. Complete activation is then carried out in the reactor as described in United States patent 4,383,095.
While the magnesium/titanium based catalyst compositions have proved to be satisfactory ethylene polymerization catalysts, there is a continuing effort to improve on the catalysis aspect of ethylene polymerization and, more particularly, to improve the technique for catalyst activation.
Disclosure of the Invention An object of this invention, therefore, is to provide a process for the activation of known ethylene polymerization catalysts, such as titanium D-14,119 ~2~ 7 or vansdium compounds, whereby an activated catalyst is prepared much more rapidly and simply than by following the route to the activated magnesium/
titanium based cstalyst composition heretofore discussed.
Other ob~ects and advantages will become apparent hereafter.
According to the present invention, process for activating a titanium or vanadium compound and producing polyethylene has been discovered comprising (i) dissolving a divalent magnesium halide and a Lewis acid having the formula RmAlXn or RmBXn wherein R is an alkyl or aromatic radical, each radical having 1 to 12 carbon atoms and each R being alike or different; X is a halogen atom; m is an integer from 0 to 3; and m+n equals 3, in an excess of electron donor compound selected from the group consisting of alkyl esters of alkyl snd aromatic carboxylic acids and alkyl and cycloalkyl ethers, each compound having 2 to 12 carbon atoms, in such a manner that a magnesium halidelLewis acid/electron donor complex is formed;
(ii) separating the complex from excess electron donor compound; and (iii) introducing (a) the complex, the titanium or vanadium compound, and a hydrocarbyl aluminum compound and (b) ethylene into a reactor in such a manner that the titanium or vanadium compound is activated and polyethylene is produced.
Detailed DescriPtion Titanium or vanadium compounds of lnterest here are commonly used as catalyst components in the `` ~269~7 polymerization of ethylene. Typical titanium compounds have the formula Ti(OR)nX4_n wherein R
is a hydrocarbyl group having 1 to 14 carbon atoms or a COR' radical wherein R' is a hydrocarbyl group having 1 to 14 carbon atoms; X is a halide radical;
and n is an integer from 0 to 4. Examples of titanium compounds are TiCl4; TiBr4; TiI4;
Ti(OCH3)C13; Ti(OC6H5)C13;
Ti(OCOCH3)C13; Ti(OCOC6H5)C13; Ti(OC2H5)C13;
( C2H5)2Cl2; Ti(C3H7)2C12; Ti(OC2H5)3Cl;
Ti(OC6H5)3Cl, Ti(OC2H5)4; Ti(oC3H7)4;
Ti(oC4Hg)4; Ti(oC6H13)4, Ti(OC6Hll)4;
( 8H17)4; Ti(CH2(C2H5) CHC4Hg)4;
Ti(OCgH19)4; Ti[OC6H3(CH3)2]4;
( 3)2(OC4H9)2; Ti(OC3H7)3(OC4Hg);
( 2 5)2(OC4Hg)2; Ti(OC2H4OCH3)4; and Ti~OC2H4Cl)4. Examples of vanadium compounds are VC14, VC13, VOCl3, triisobutyl vanadate, and vanadiumltris-acetyl acetonate. Other suitable vanadium compounds are mentioned in United States patents 3,956,255 and 4,370,455.
The electron donor solvents used in the process are organic compounds, liquid at temperatures in the range of about 0C to about 200C, in which the magnesium halide and defined Lewis acids are soluble. The electron donor solvents are also known as Lewis bases.
The electron donor compounds are selected from the group consisting of alkyl esters of alkyl and aromatic carboxylic acids and alkyl and cycloalkyl ethers, each compound having 2 to 12 D-14,119 ~Z~9~7 carbon atoms. Among these electron donor compounds the preferable ones are alkyl esters of saturated alkyl carboxylic acids having 1 to 4 csrbon atoms;
alkyl esters of aromatic carboxylic acids having 7 or 8 carbon atoms; alkyl ethers having 2 to 8 carbon atoms, preferably 4 or 5 carbon atoms; and cycloalkyl ethers having 4 or 5 carbon atoms;
preferably mono- or di-ethers having 4 c~rbon atoms. The most preferred of these electron donor compounds include methyl formate, ethyl acetate, butyl acetate, ethyl ether, tetrahydrofuran, and dioxane. Other examples of electron donor compounds are di-n-propy~ ether, dibutyl ether, ethyl formate, methyl acetate, ethyl anisate, ethylene carbonate, tetrahydropyran, and ethyl propionate.
The divalent magnesium halide can be represented by the formula MgX2 wherein X ~s selected from the group consisting of Cl, Br, and I.
Suitable magnesium compounds include MgC12, MgBr2, and MgI2. Anhydrous MgC12 is particularly preferred.
The Lewis acids are, as noted above, those having the formula RmAlXn or RmBXn wherein R is an alkyl or aromatic radical, each radical having 1 to 12 carbon stoms and each R being alike or different; X is a halogen atom; M is an integer from O to 3; n is an integer from O to 3; and m+n equals 3. Examples of alkyl radicals are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, ~l269~7 pentyl, neopentyl, hexyl, 2-methylpentyl, heptyl, octyl, isooctyl, 2-ethylhexyl, 5,5-dimethylhexyl, nonyl, decyl, isodecyl, undecyl, and dodecyl.
Example of aromatic radicals are: phenyl, phenethyl, methoxyphenyl, benzyl, tolyl, xylyl, naphthyl, naphthal, and methylnaphthyl. Examples of halogens are chlorine, bromine, and iodine.
Preferred Lewis acids are AlC13,
2 5 1C12' (C2H5)2AlCl~ (C2H5)3Al, and BC13 Other examples o~ suitable Lewis acids are triisobutyl aluminum, tributylaluminum, dibutyl-aluminum chloride, diethylaluminum bromide, propyl-aluminum dichloride, butylaluminum dibromide, (C6H13)3' Al(C8H17)3- trimethylaluminum~
diisobutylaluminum chloride, isobutylaluminum dichloride, diethylaluminum methoxide, diethylaluminum ethoxide, dimethylaluminum chloride, and methylaluminum dichloride.
The magnesium halide/Lewis acid/electron donor complex, which may also be referred to as an adduct or solvated adduct, is formed when the divalent magnesium halide is dissolved in an electron donor together with a Lewis acid at a temperature in the range of about 0C to about 200C. The molar ratio of magnesium halide to Lewis acid csn be in the range of sbout 0.1 mole to about 4 moles oF magnesium halide to one mole of Lewis Acid and is preferably in the range of about 0.5 mole to about 2 moles of magnesium halide to one mole of Lewis Acid. An excess of electron donor compound, i.e., a number of moles of electron donor compound at least about 15 times greater than the ~269~7 total number of moles of magnesium halide and Lewis Acid combined, provides a sufficient number of moles of electron donor to yield the complex. While atmospheric pressure is generally used, pressure is not considered a significant factor. These solvated adducts can be isolated by evaporation of excess solvent or by slow cryst~llization of the adduct after partial concentration of the solvent.
Preferred complexes are derived from MgC12 and the Lewis acids AlC13, C2H5AlC12, (C2H5)2AlCl, (C2H5)3 BC13. These complexes are as follows:
MgC12-2AlC13-nTHF MgC12-2AlC13-nEtOAC
MgC12-2EADC-nTHF MgC12-2BC13-6E~OAC
MgC12-EADC-nTHF MgC12-2EADC-nEtOAC
2MgC12-TEAL-nTHF
wherein n can be an integer from 1 to 13 and is preferably an integer from 5 to 12. The integer represents the number of moles of electron donor compound.
The following acronyms are used above and throughout this specification:
EADC = ethylaluminum dichloride THF = tetrahydrofuran TEAL = triethylaluminum EtOAC = ethyl acetate DEAC = diethylaluminum chloride Analyses of six of the complexes are set forth in Table I.
- ~2~
TABLE I
Analyzed Holar Analyses (wei~ht %) Stoichiometries ComPlex H~ Al B M~ Al B
HgC12-2AlCl3~nTHF2.14 5.46 _ 1 2.27 MgC12-2EADC-nTHF 2.74 6.71 - 1 2.20 H~Cl2-EADConTHF 4.44 5.25 - 1 1.06 2M~Cl2-TEAL-nTHF 6.48 3.56 - 2.02 HsCl2-2BCl3-6EtOAC3.01 - 2.79 1 - 2.04 ~Cl2-2EADC-nEtOAC 2.42 5.57 - 1 2.07 ~26~ 7 g The family of sub~ect complexes is found to activate titanium or vanadium compounds, particularly titanium tetrachloride, in the presence of a hydrocarbyl aluminum compound as a cocatalyst, in ethylene gas phase or slurry polymerizstion reactions. A catalyst, prepared by slurrying one of these complexes with titanium tetrachloride in hexane (or another inert hydrocarbon solvent), followed by washing with excess hexane and drying under reduced pressure possesses excellent acti~ity in hexane polymerization reactions employing triethyl aluminum as a cocatalyst.
The hydrocarbyl aluminum cocatalyst can be represented by the formula R3Al wherein each R is an alkyl, cycloalkyl, sryl, or hydride radical; at least one R is a hydrocarbyl radical; two or three R
radicals can be ~oined in a cyclic radical forming a heterocyclic structure; each R can be alike or different; and each R, ~hich is a hydrocarbyl radical, has 1 to 20 carbon atoms, and preferably 1 to 10 carbon atoms. Further, each alkyl radical can be straight or branched chain and such hydrocarbyl radical can be a mixed radical, i.e., the radical can contain alkyl, aryl, and/cr cycloalkyl groups.
Examples of suitable radicals are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, 2-methylpentyl, heptyl, octyl, isooctyl, 2-ethylhexyl, 5,5-dimethylhexyl, nonyl, decyl, isodecyl, undecyl, dodecyl, phenyl, phenethyl, methoxyphenyl, benzyl, tolyl, xylyl, naphthyl, naphthal, methylnaphthyl, cycohexyl, cycloheptyl, and cyclooctyl.
~2~9~7 Examples of hydrocarbyl aluminum compounds are as follows: triisobutylaluminum, trihexyl-aluminum, di-isobutylaluminum hydride, dihexyl-aluminum hydride, isobutylaluminum dihydride, hexyl-aluminum dihydride, di-isobutylhexylaluminum, isobutyl dihexylaluminum, trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, trioctylaluminum, tridecylaluminum, tridodecylaluminum, tribenzylaluminum, triphenylaluminum, trinaphthylaluminum, and tritolylaluminum. The preferred hydrocarbyl aluminums are triethylaluminum, triisobutylaluminum, trihexylaluminum, di-isobutylaluminum hydride, and dihexylaluminum hydride.
These complexes also activate titanium or vanadium compounds when the complex is first impregnated on a silica support. The purpose of the impregnation is to produce polymers of preferred shape and bulk density. To achieve this end, the magnesium halide and Lewis acid are dissolved in the electron donor solvent and slurried with the silica support. The excess solvent is then removed by purging or evaporation under reduced pressure. The resulting impregnated complexes are slurried with, for example, the tetravalent titanium compound in hexane, followed by washing with excess hexane and drying, as sbove. These impregnated catalysts are also found to be active wlth triethyl aluminum as a cocatalyst. The result of the copolymerization is not only high catalyst activity, but high bulk density as well.
~6~7 Further, it is found that the solubility of the divalent magnesium halide in the electron donor solvent is increased by the presence of the defined Lewis acid, e.g., the degree of solubility of MgC12 in tetrahydrofuran is increased 100 percent by using a 0.6 molar solution of triethylaluminum in tetrahydrofuran.
Conductivity experiments measure the ability of a solution to csrry a charge across a fixed path between two electrodes. If the bonding interaction between the magnesium halide and the Lewis acid in the electron donor solvent is ionic then a significant increase in conductivity over each component alone in the electron donor solvent should occur. The results of a series of conductivity experiments indicate ~ust such an increase and it is therefore concluded that the sub;ect complex is ionic in character. Since the conductive capacity is reached almost immediately upon mixing the components, there apparently is no kinetic barrier to interaction of the magnesium halide and Lewis acid in the electron donor solvent.
Impregnation of sub~ect complex into, for example, silic8 prior to its use in titanium or vanadium compound activation is desirable to provide improved particle morphology. The impregnation is accomplished by mixing the complex and silica gel in the electron donor solvent followed by solvent removal under reduced pressure. Ethylene polymerization reactions are run by either slurrying the silica gel supported complex with the tetravalent titanium compound or isolating the ~Z~ }7 impregnated silica gel after treatment with the tetravalent titanium compound, and then using the slurry or isolated precursor in the polymeri2ation reaction. It is found that the levels of catalyst activity, resin properties, snd bulk densities compare favorably with catalysts exemplified by the reaction product of magnesium dichloride/titanium tetrachloride/tetrahydrofuran and triethyl aluminum.
The invention is illustrated by the following examples:
Complexes are formed when magnesium dichloride and a defined Lewis acid are dissolved in an excess of electron donor solvent. The solvated complex is isolated by evaporation of excess solvent or slow crystallization after partial evaporation of the solvent. The complex is either (1) slurried with titanium tetrachloride in hexane to form a precursor, which is then isolated, or (2) slurried with titanium tetrachloride in hexane just prior to introduction into the polymerization reactor.
Example 1 The complex MgC12/2EADC/THF is prepared as follows: to a flask is added 1.93 grams (15 millimoles~ of ethylaluminum dichloride. After chilling to 0C, one cubic centimeter of THF is added and the solid dissolves immediately. After warming to room temperature, 9 cubic centimeters of 0.51 molar MgC12 in THF is added and a white precipitate forms immediately. The mixture is warmed to 40C and all of the solid dissolves. Upon cooling to ambient temperature, the precipitate ~Z69~ 7 reforms. The mixture is cooled to 0C and the mother liquor is decanted away. The residue is then washed with cold THF and dried under high vacuum.
Analysis of complex:
6.71% by weight aluminum 2.74% by weight magnesium Proton nuclear magnetic resonance (CH2C12, chemical shift in parts per million):
minus 0.15 quartet; 0.83 triplet; 1.80 multiplet,
diisobutylaluminum chloride, isobutylaluminum dichloride, diethylaluminum methoxide, diethylaluminum ethoxide, dimethylaluminum chloride, and methylaluminum dichloride.
The magnesium halide/Lewis acid/electron donor complex, which may also be referred to as an adduct or solvated adduct, is formed when the divalent magnesium halide is dissolved in an electron donor together with a Lewis acid at a temperature in the range of about 0C to about 200C. The molar ratio of magnesium halide to Lewis acid csn be in the range of sbout 0.1 mole to about 4 moles oF magnesium halide to one mole of Lewis Acid and is preferably in the range of about 0.5 mole to about 2 moles of magnesium halide to one mole of Lewis Acid. An excess of electron donor compound, i.e., a number of moles of electron donor compound at least about 15 times greater than the ~269~7 total number of moles of magnesium halide and Lewis Acid combined, provides a sufficient number of moles of electron donor to yield the complex. While atmospheric pressure is generally used, pressure is not considered a significant factor. These solvated adducts can be isolated by evaporation of excess solvent or by slow cryst~llization of the adduct after partial concentration of the solvent.
Preferred complexes are derived from MgC12 and the Lewis acids AlC13, C2H5AlC12, (C2H5)2AlCl, (C2H5)3 BC13. These complexes are as follows:
MgC12-2AlC13-nTHF MgC12-2AlC13-nEtOAC
MgC12-2EADC-nTHF MgC12-2BC13-6E~OAC
MgC12-EADC-nTHF MgC12-2EADC-nEtOAC
2MgC12-TEAL-nTHF
wherein n can be an integer from 1 to 13 and is preferably an integer from 5 to 12. The integer represents the number of moles of electron donor compound.
The following acronyms are used above and throughout this specification:
EADC = ethylaluminum dichloride THF = tetrahydrofuran TEAL = triethylaluminum EtOAC = ethyl acetate DEAC = diethylaluminum chloride Analyses of six of the complexes are set forth in Table I.
- ~2~
TABLE I
Analyzed Holar Analyses (wei~ht %) Stoichiometries ComPlex H~ Al B M~ Al B
HgC12-2AlCl3~nTHF2.14 5.46 _ 1 2.27 MgC12-2EADC-nTHF 2.74 6.71 - 1 2.20 H~Cl2-EADConTHF 4.44 5.25 - 1 1.06 2M~Cl2-TEAL-nTHF 6.48 3.56 - 2.02 HsCl2-2BCl3-6EtOAC3.01 - 2.79 1 - 2.04 ~Cl2-2EADC-nEtOAC 2.42 5.57 - 1 2.07 ~26~ 7 g The family of sub~ect complexes is found to activate titanium or vanadium compounds, particularly titanium tetrachloride, in the presence of a hydrocarbyl aluminum compound as a cocatalyst, in ethylene gas phase or slurry polymerizstion reactions. A catalyst, prepared by slurrying one of these complexes with titanium tetrachloride in hexane (or another inert hydrocarbon solvent), followed by washing with excess hexane and drying under reduced pressure possesses excellent acti~ity in hexane polymerization reactions employing triethyl aluminum as a cocatalyst.
The hydrocarbyl aluminum cocatalyst can be represented by the formula R3Al wherein each R is an alkyl, cycloalkyl, sryl, or hydride radical; at least one R is a hydrocarbyl radical; two or three R
radicals can be ~oined in a cyclic radical forming a heterocyclic structure; each R can be alike or different; and each R, ~hich is a hydrocarbyl radical, has 1 to 20 carbon atoms, and preferably 1 to 10 carbon atoms. Further, each alkyl radical can be straight or branched chain and such hydrocarbyl radical can be a mixed radical, i.e., the radical can contain alkyl, aryl, and/cr cycloalkyl groups.
Examples of suitable radicals are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, 2-methylpentyl, heptyl, octyl, isooctyl, 2-ethylhexyl, 5,5-dimethylhexyl, nonyl, decyl, isodecyl, undecyl, dodecyl, phenyl, phenethyl, methoxyphenyl, benzyl, tolyl, xylyl, naphthyl, naphthal, methylnaphthyl, cycohexyl, cycloheptyl, and cyclooctyl.
~2~9~7 Examples of hydrocarbyl aluminum compounds are as follows: triisobutylaluminum, trihexyl-aluminum, di-isobutylaluminum hydride, dihexyl-aluminum hydride, isobutylaluminum dihydride, hexyl-aluminum dihydride, di-isobutylhexylaluminum, isobutyl dihexylaluminum, trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, trioctylaluminum, tridecylaluminum, tridodecylaluminum, tribenzylaluminum, triphenylaluminum, trinaphthylaluminum, and tritolylaluminum. The preferred hydrocarbyl aluminums are triethylaluminum, triisobutylaluminum, trihexylaluminum, di-isobutylaluminum hydride, and dihexylaluminum hydride.
These complexes also activate titanium or vanadium compounds when the complex is first impregnated on a silica support. The purpose of the impregnation is to produce polymers of preferred shape and bulk density. To achieve this end, the magnesium halide and Lewis acid are dissolved in the electron donor solvent and slurried with the silica support. The excess solvent is then removed by purging or evaporation under reduced pressure. The resulting impregnated complexes are slurried with, for example, the tetravalent titanium compound in hexane, followed by washing with excess hexane and drying, as sbove. These impregnated catalysts are also found to be active wlth triethyl aluminum as a cocatalyst. The result of the copolymerization is not only high catalyst activity, but high bulk density as well.
~6~7 Further, it is found that the solubility of the divalent magnesium halide in the electron donor solvent is increased by the presence of the defined Lewis acid, e.g., the degree of solubility of MgC12 in tetrahydrofuran is increased 100 percent by using a 0.6 molar solution of triethylaluminum in tetrahydrofuran.
Conductivity experiments measure the ability of a solution to csrry a charge across a fixed path between two electrodes. If the bonding interaction between the magnesium halide and the Lewis acid in the electron donor solvent is ionic then a significant increase in conductivity over each component alone in the electron donor solvent should occur. The results of a series of conductivity experiments indicate ~ust such an increase and it is therefore concluded that the sub;ect complex is ionic in character. Since the conductive capacity is reached almost immediately upon mixing the components, there apparently is no kinetic barrier to interaction of the magnesium halide and Lewis acid in the electron donor solvent.
Impregnation of sub~ect complex into, for example, silic8 prior to its use in titanium or vanadium compound activation is desirable to provide improved particle morphology. The impregnation is accomplished by mixing the complex and silica gel in the electron donor solvent followed by solvent removal under reduced pressure. Ethylene polymerization reactions are run by either slurrying the silica gel supported complex with the tetravalent titanium compound or isolating the ~Z~ }7 impregnated silica gel after treatment with the tetravalent titanium compound, and then using the slurry or isolated precursor in the polymeri2ation reaction. It is found that the levels of catalyst activity, resin properties, snd bulk densities compare favorably with catalysts exemplified by the reaction product of magnesium dichloride/titanium tetrachloride/tetrahydrofuran and triethyl aluminum.
The invention is illustrated by the following examples:
Complexes are formed when magnesium dichloride and a defined Lewis acid are dissolved in an excess of electron donor solvent. The solvated complex is isolated by evaporation of excess solvent or slow crystallization after partial evaporation of the solvent. The complex is either (1) slurried with titanium tetrachloride in hexane to form a precursor, which is then isolated, or (2) slurried with titanium tetrachloride in hexane just prior to introduction into the polymerization reactor.
Example 1 The complex MgC12/2EADC/THF is prepared as follows: to a flask is added 1.93 grams (15 millimoles~ of ethylaluminum dichloride. After chilling to 0C, one cubic centimeter of THF is added and the solid dissolves immediately. After warming to room temperature, 9 cubic centimeters of 0.51 molar MgC12 in THF is added and a white precipitate forms immediately. The mixture is warmed to 40C and all of the solid dissolves. Upon cooling to ambient temperature, the precipitate ~Z69~ 7 reforms. The mixture is cooled to 0C and the mother liquor is decanted away. The residue is then washed with cold THF and dried under high vacuum.
Analysis of complex:
6.71% by weight aluminum 2.74% by weight magnesium Proton nuclear magnetic resonance (CH2C12, chemical shift in parts per million):
minus 0.15 quartet; 0.83 triplet; 1.80 multiplet,
3.90 multiplet. This spectrum is uniquely different from any of the starting materials.
Example 2 - The complex MgC12/EADC/THF is prepared as follows: to a flask is added 1.94 grams (15 millimoles) of ethyl aluminum dichloride. After cooling the flask to 0C, 13.3 cubic centimeters of 0.52 molar MgC12 (6.9 millimoles) in THF is added. The solution is concentrated to 5 cubic centimeters and a crop of crystals is collected by decanting away the mother liquor. The mother liquor is allowed to stand and a second crop of crystals is collected.
Analysis of complex (second crop of crystals):
5.25% by weight aluminum
Example 2 - The complex MgC12/EADC/THF is prepared as follows: to a flask is added 1.94 grams (15 millimoles) of ethyl aluminum dichloride. After cooling the flask to 0C, 13.3 cubic centimeters of 0.52 molar MgC12 (6.9 millimoles) in THF is added. The solution is concentrated to 5 cubic centimeters and a crop of crystals is collected by decanting away the mother liquor. The mother liquor is allowed to stand and a second crop of crystals is collected.
Analysis of complex (second crop of crystals):
5.25% by weight aluminum
4.44% by weight magnesium Infrared spectrum (Nujol* mull; cm 1), ether absorptions only: 1025; 1015; 875; 862; 848.
As in example 1, this spectrum is uniquely different from any of the starting materials.
* Trademark D-14,119 ~Z6~}7 ExamPle 3 The complex MgG12/2 EADC/EtOAC is prepared as follows: to a flask is added 1.9 grams (15 milli~oles) of ethyl aluminum dichloride with 8 cubic centimeters of 0.52 molar MgC12 in EtOAC. A
precipitate forms immediately. The mixture is warmed and allowed to cool slowly. A white solid forms snd is collected by decanting away the mo~her liquor. The remaining solid is cooled and washed two times with cold EtOAC.
Analysis:
2.42 % by weight magnesium
As in example 1, this spectrum is uniquely different from any of the starting materials.
* Trademark D-14,119 ~Z6~}7 ExamPle 3 The complex MgG12/2 EADC/EtOAC is prepared as follows: to a flask is added 1.9 grams (15 milli~oles) of ethyl aluminum dichloride with 8 cubic centimeters of 0.52 molar MgC12 in EtOAC. A
precipitate forms immediately. The mixture is warmed and allowed to cool slowly. A white solid forms snd is collected by decanting away the mo~her liquor. The remaining solid is cooled and washed two times with cold EtOAC.
Analysis:
2.42 % by weight magnesium
5.57% by weight aluminum HlNMR (nuclear magnetic resonance) spectrum (CH2C12, chemical shift in parts per million): minus 0.05 quartet; 0.95 triplet;
1.17 triplet; 2.14 singlet; 4.14 quartet.
This spectrum is also uniquely different from any of the starting materials.
ExamPle 4 The complex MgC12/2 BC13/EtOAC is prepared as follows: to a flask are added equal volumes of 0.13 molar MgC12 and BC13 solutions in ethyl acetate. A white precipitate forms immediately snd is isolated by filtration.
Analysis:
3.01% by weight magnesium 2.79% by weight boron 34.7% by weight chlorine ~2~9~7 ExamPles 5 to 8 The catalyst in examples 5 to 8 is prepared by isolating an adduct formed by slurrying the complex with an excess of TiC14 in hexane. The titanium derivative is isolated by decanting away the hexane solution and washing the residue with excess hexane. Additional steps, conditions, and results will be found below and in Table II.
ExamPle 9 The complex is slurried with 7 milligrsms of TiCl4 ~ust prior to addition to the polymerization reaction. Additional steps, conditions, snd results will be found below and in Table II.
Examples 10 and 11 (a) To a flask is added 12.67 grams of silica, which has been dried under a nitrogen purge at 800C. To the silic8 iS added 75 cubic centimeters of THF followed by 5.9 cubic centimeters of 1.5 molar EADC in hexane (8.85 millimoles).
Next, 8.5 cubic centimeters of 0.52 molar MgC12 in THF is added. After stirring, the solvent is removed under reduced pressure.
(b) To a flask is charged 5.48 grams of the supported complex with 20 cubic centimeters of hexane. To this is added 0.35 millimoles of TiCl4 per gram of supported complex. The mixture is stirred, allowed to settle, and the solvent is decanted sway. The solid is washed three times with hexane, then dried under vacuum. Additional steps, ~Z~93~7 conditions, and results will be found below and in Table II.
ExamPles 12 and 13 Example 10 is repeated except that DEAC is substituted for EADC. Additional steps, conditions, and results will be found below and in Table II.
Each catalyst of examples 5 to 13 and TEAL
as a cocatalyst are added to a reaction vessel containing 20 cubic centimeters of l-hexene.
Ethylene is introduced at an initial pressure of 0.89 megaPascal. Hydrogen is also introduced at 0.14 megaPascal. The resction temperature is 85C.
Table II sets forth the following conditions and results:
1. The isolated magnesium halide/Lewis acid/electron donor complex. Milligrams of catalyst are set forth in parentheses. In examples 10 to 13, this weight includes the support.
2. The method of titanium addition, i.e., (1) or (2) described above. In method (2), the milligrams of titanium added in examples 9, 11, and 13 are 7, 6.9, and 6.9, respectively.
3. The percentage of titanium in the catalyst.
4. Triethylaluminum is used as a cocatalyst. The mole ratio of triethylaluminum to titanium is given.
5. The activity of the catalyst in kilograms of polyethylene per millimole of titanium per hour at an ethylene pressure of one megaPascal.
~Z693~7
1.17 triplet; 2.14 singlet; 4.14 quartet.
This spectrum is also uniquely different from any of the starting materials.
ExamPle 4 The complex MgC12/2 BC13/EtOAC is prepared as follows: to a flask are added equal volumes of 0.13 molar MgC12 and BC13 solutions in ethyl acetate. A white precipitate forms immediately snd is isolated by filtration.
Analysis:
3.01% by weight magnesium 2.79% by weight boron 34.7% by weight chlorine ~2~9~7 ExamPles 5 to 8 The catalyst in examples 5 to 8 is prepared by isolating an adduct formed by slurrying the complex with an excess of TiC14 in hexane. The titanium derivative is isolated by decanting away the hexane solution and washing the residue with excess hexane. Additional steps, conditions, and results will be found below and in Table II.
ExamPle 9 The complex is slurried with 7 milligrsms of TiCl4 ~ust prior to addition to the polymerization reaction. Additional steps, conditions, snd results will be found below and in Table II.
Examples 10 and 11 (a) To a flask is added 12.67 grams of silica, which has been dried under a nitrogen purge at 800C. To the silic8 iS added 75 cubic centimeters of THF followed by 5.9 cubic centimeters of 1.5 molar EADC in hexane (8.85 millimoles).
Next, 8.5 cubic centimeters of 0.52 molar MgC12 in THF is added. After stirring, the solvent is removed under reduced pressure.
(b) To a flask is charged 5.48 grams of the supported complex with 20 cubic centimeters of hexane. To this is added 0.35 millimoles of TiCl4 per gram of supported complex. The mixture is stirred, allowed to settle, and the solvent is decanted sway. The solid is washed three times with hexane, then dried under vacuum. Additional steps, ~Z~93~7 conditions, and results will be found below and in Table II.
ExamPles 12 and 13 Example 10 is repeated except that DEAC is substituted for EADC. Additional steps, conditions, and results will be found below and in Table II.
Each catalyst of examples 5 to 13 and TEAL
as a cocatalyst are added to a reaction vessel containing 20 cubic centimeters of l-hexene.
Ethylene is introduced at an initial pressure of 0.89 megaPascal. Hydrogen is also introduced at 0.14 megaPascal. The resction temperature is 85C.
Table II sets forth the following conditions and results:
1. The isolated magnesium halide/Lewis acid/electron donor complex. Milligrams of catalyst are set forth in parentheses. In examples 10 to 13, this weight includes the support.
2. The method of titanium addition, i.e., (1) or (2) described above. In method (2), the milligrams of titanium added in examples 9, 11, and 13 are 7, 6.9, and 6.9, respectively.
3. The percentage of titanium in the catalyst.
4. Triethylaluminum is used as a cocatalyst. The mole ratio of triethylaluminum to titanium is given.
5. The activity of the catalyst in kilograms of polyethylene per millimole of titanium per hour at an ethylene pressure of one megaPascal.
~Z693~7
6. Melt index: ASTM D-1238, Condition E. Measured at 190C and reported as grams per 10 minutes.
7. Melt flow ratio: Ratio of Flow Index to Melt Index. Flow index: ASTM D-1238, Condition F. Measured at 10 times the weight used in the melt index test above.
8. Polymer density: ASTM D-1505 procedure is followed for polymers having a density of less than 0.940 gram per cubic centimeter and a modified procedure is used for polymers having a density equal to or greater than 0.940 gram per cubic centimeter. For the low density polymers, a plaque is made and conditioned for one hour at 100C
to approach equilibrium crystallinity. For the high density polymers, the plaque is conditioned for one hour at 120C to approach equilibrium crystallinity, and is then quickly cooled to room temperature.
Measurement for density is then made in a density gradient column and density values are reported as grams per cubic centimeter.
to approach equilibrium crystallinity. For the high density polymers, the plaque is conditioned for one hour at 120C to approach equilibrium crystallinity, and is then quickly cooled to room temperature.
Measurement for density is then made in a density gradient column and density values are reported as grams per cubic centimeter.
9. Polymer bulk density: ASTM D-1895, Method B. The resin is poured via a 3/8 inch diameter funnel into a 400 milliliter graduated cylinder to the 400 milliliter line without shaking the cylinder, and weighed by difference. Density values are reported as kilograms per cubic meter.
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Claims (4)
1. A process for activating a titanium or vanadium compound and producing polyethylene comprising (i) dissolving a divalent magnesium halide and a Lewis acid having the formula RmA1Xn or RmBXn wherein R is an alkyl or aromatic radical, each radical having 1 to 12 carbon atoms and each R being alike or different; X is a halogen atom; m is an integer from 0 to 3; n is an integer from 0 to 3; and m+n equals 3, in an excess of electron donor compound selected from the group consisting of alkyl esters of alkyl and aromatic carboxylic acids and alkyl and cycloalkyl ethers, each compound having 2 to 12 carbon atoms, in such a manner that a magnesium halide/Lewis acid/electron donor complex is formed; (ii) separating the complex from excess electron donor compound; and (iii) introducing (a) the complex, the titanium or vanadium compound, and A hydrocarbyl aluminum compound and (b) ethylene into a reactor in such a manner that the titanium or vanadium compound is activated and polyethylene is produced.
2. The process defined in claim 1 wherein the halide is divalent magnesium chloride.
3. The process defined in claim 1 wherein the Lewis acid is selected from the group consisting A1C13, C2H5A1C12, (C2H5)2A1C1. (C2H5)3 A1, and BC13.
4. The process defined in claim 3 wherein the electron donor compound is selected from the group consisting of methyl formate, ethyl acetate, butyl acetate, ethyl ether, tetrahydrofuran, and dioxane.
D-14,119
D-14,119
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000590390A CA1296346C (en) | 1986-02-27 | 1989-02-07 | Process for activation of titanium and vanadium catalysts useful in ethylene polymerization |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/833,148 US4670526A (en) | 1986-02-27 | 1986-02-27 | Process for activation of titanium and vanadium catalysts useful in ethylene polymerization |
| US833,148 | 1986-02-27 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000590390A Division CA1296346C (en) | 1986-02-27 | 1989-02-07 | Process for activation of titanium and vanadium catalysts useful in ethylene polymerization |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1269197A true CA1269197A (en) | 1990-05-15 |
Family
ID=25263569
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000530090A Expired - Lifetime CA1269197A (en) | 1986-02-27 | 1987-02-19 | Process for activation of titanium and vanadium catalysts useful in ethylene polymerization |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4670526A (en) |
| EP (1) | EP0234574B1 (en) |
| JP (1) | JPS62253605A (en) |
| AT (1) | ATE66680T1 (en) |
| CA (1) | CA1269197A (en) |
| DE (1) | DE3772405D1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI89066C (en) * | 1989-11-20 | 1993-08-10 | Neste Oy | FOERFARANDE FOER FRAMSTAELLNING AV EN POLYMERISERINGSKATALYTKONPONENT FOER OLEFINER, EN POLYMERISERINGSKATALYTKONPONENT FRAMSTAELLD MED FOERFARANDET OCH DESS BRUK |
| US5034361A (en) * | 1990-05-24 | 1991-07-23 | Shell Oil Company | Catalyst precursor production |
| FI86989C (en) * | 1990-12-19 | 1992-11-10 | Neste Oy | Process for producing a polymerization catalyst component for olefins, a polymerization catalyst component prepared by the process, and its use |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3409681A (en) * | 1964-06-25 | 1968-11-05 | Exxon Research Engineering Co | Method of making novel bimetallic heterogeneous catalysts and their use in hydrocarbon conversions |
| JPS5719122B2 (en) * | 1973-12-26 | 1982-04-21 | ||
| SE7613662L (en) * | 1975-12-10 | 1977-06-11 | Mitsui Petrochemical Ind | POLYMERIZATION OF ALFA-OLEFINES |
| JPS5287489A (en) * | 1976-01-19 | 1977-07-21 | Mitsui Petrochem Ind Ltd | Polymerization of olefins |
| JPS5910683B2 (en) * | 1978-12-11 | 1984-03-10 | 三井化学株式会社 | Polymerization method of olefins |
| US4303771A (en) * | 1978-12-14 | 1981-12-01 | Union Carbide Corporation | Process for the preparation of high density ethylene polymers in fluid bed reactor |
| JPS5770104A (en) * | 1980-10-17 | 1982-04-30 | Toa Nenryo Kogyo Kk | Catalytic component for alpha-olefin polymerization and its use |
| US4427573A (en) * | 1981-09-16 | 1984-01-24 | Union Carbide Corporation | Polymerization catalyst, process for preparing, and use for ethylene polymerization |
-
1986
- 1986-02-27 US US06/833,148 patent/US4670526A/en not_active Expired - Fee Related
-
1987
- 1987-02-19 CA CA000530090A patent/CA1269197A/en not_active Expired - Lifetime
- 1987-02-26 EP EP87102712A patent/EP0234574B1/en not_active Expired - Lifetime
- 1987-02-26 JP JP62041573A patent/JPS62253605A/en active Pending
- 1987-02-26 AT AT87102712T patent/ATE66680T1/en active
- 1987-02-26 DE DE8787102712T patent/DE3772405D1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62253605A (en) | 1987-11-05 |
| US4670526A (en) | 1987-06-02 |
| ATE66680T1 (en) | 1991-09-15 |
| EP0234574B1 (en) | 1991-08-28 |
| EP0234574A1 (en) | 1987-09-02 |
| DE3772405D1 (en) | 1991-10-02 |
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